CN110642748A - O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and synthetic method and application thereof - Google Patents
O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and synthetic method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of material, pharmaceutical and chemical synthesis, and particularly relates to an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative, and a synthesis method and application thereof. The O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative has the following structural formula:
the synthesis method comprises the steps of uniformly mixing ketoxime compounds, alpha-trifluoromethyl styrene compounds and tert-butyl hydroperoxide (TBHP) in alkali and an organic solvent I to obtain reactants, then reacting, and carrying out subsequent purification treatment after the reaction to obtain the ketoxime compounds. The method avoids using transition metal catalyst, and the used raw materials are nontoxic, cheap and easy to obtain; the reaction has good adaptability to functional groups, wide adaptability to substrates and high product yield, can be amplified to gram-scale production and synthesis, and is beneficial to industryThe product obtained by the production method has wide application in the fields of pesticides, medicines and materials.
Description
Technical Field
The invention belongs to the technical field of material, pharmaceutical and chemical synthesis, and particularly relates to an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative, and a synthesis method and application thereof.
Background
Since the atomic radius of fluorine atoms is small and close to that of hydrogen atoms, but has high electronegativity, it is difficult to polarize. Therefore, introduction of fluorine atoms or fluorine-containing groups into organic compound molecules generally significantly improves chemical properties, physical properties, and biological activity of the compounds. According to statistics, more than 30% of pesticide or drug molecules sold in the market contain at least one fluorine atom or fluorine-containing group. However, the types of natural products containing fluorine which exist in nature are very limited. In order to meet the urgent need of production and research on the increase of the number and the types of the organic fluorine-containing compounds, the development of a method for efficiently synthesizing the organic fluorine-containing compounds is one of the core tasks to be solved urgently by chemists.
In view of the important application value of oxime ether compounds in the fields of pesticides and medicines, research on efficient synthesis methods of oxime ether compounds has been receiving wide attention. However, O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives and synthetic methods thereof have not been reported, and research on the compounds and synthetic techniques thereof is still blank. Therefore, the development of a method for efficiently synthesizing O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives is still a challenging research topic.
Disclosure of Invention
In order to solve the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative.
Another object of the present invention is to provide a method for efficiently synthesizing the above-mentioned O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative.
The invention also aims to provide application of the O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative has the following structure:
wherein R is1Is phenyl, p-bromophenyl, p-chlorophenyl, m-chlorophenyl, o-chlorophenyl, p-fluorophenyl, m-fluorophenyl, o-fluorophenyl, p-iodophenyl, p-tolyl (p-methylphenyl), m-tolyl, p-methoxyphenyl, m-methoxyphenyl, p-methylthiophenyl, p-trifluoromethylphenyl, p-methylsulfonylphenyl, p-carbomethoxyphenyl, p-cyanophenyl, 3, 4-dimethylphenyl, 3, 4-methylenedioxyphenyl, styryl, 1-tetrahydronaphthyl, 2-naphthyl, 2-furyl, 2-thienyl or 2-pyridyl;
R2is phenyl, methyl, ethyl or tert-butyl;
R3is phenyl, p-bromophenyl, p-chlorophenyl, p-fluorophenyl, p-tolyl (p-methylphenyl), p-methoxyphenyl, p-trifluoromethylphenyl, p-tert-butylphenyl, p-morpholinophenyl, 3, 4-dimethylphenyl, 2-naphthyl, 3-benzothienyl or 3-pyridyl.
Preferably, the O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative has any one of the following structural formulas:
the invention further provides a synthetic method of the O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative, which comprises the following steps: in alkali and organic solvent I, uniformly mixing ketoxime compound, alpha-trifluoromethyl styrene compound and tert-butyl hydroperoxide (TBHP) to obtain reactant, then reacting, and carrying out subsequent purification treatment after reaction to obtain the O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative.
Preferably, the ketoxime compound is
Preferably, the alpha-trifluoromethyl styrene compound is
Preferably, the base is one or more of cesium carbonate, potassium tert-butoxide, lithium tert-butoxide and sodium tert-butoxide.
Preferably, the organic solvent I is one or more than two of N, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, N-methylpyrrolidone and acetonitrile.
Preferably, in the reactant, the molar ratio of the ketoxime compound to the alpha-trifluoromethylstyrene compound is 1: 1-1: 3.
More preferably, in the reactant, the molar ratio of the ketoxime compound to the alpha-trifluoromethylstyrene compound is 1: 1.5.
Preferably, in the reactant, the molar ratio of the ketoxime compound to tert-butyl hydroperoxide (TBHP) is 1: 1-1: 3.
More preferably, the molar ratio of the ketoxime compound to tert-butyl hydroperoxide (TBHP) in the reactants is 1: 1.5.
Preferably, in the reactant, the molar ratio of the ketoxime compound to the alkali is 1: 1-1: 3.
More preferably, in the reactant, the molar ratio of the ketoxime compound to the alkali is 1: 1.5.
Preferably, the reaction temperature is room temperature, the reaction time is 12h, and the reaction is carried out in air or nitrogen atmosphere.
Preferably, the subsequent purification treatment refers to adding water and an organic solvent II after the reaction is finished, extracting the reaction solution, performing reduced pressure rotary evaporation on an organic layer to remove the solvent to obtain a crude product, and performing column chromatography purification to obtain the O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative.
More preferably, the organic solvent II is ethyl acetate, dichloromethane or diethyl ether.
More preferably, the column chromatography purification refers to the purification of the crude product by using petroleum ether: and (3) performing column chromatography purification by using a mixed solvent of ethyl acetate as an eluent, wherein the weight ratio of petroleum ether: the volume ratio of the ethyl acetate is (5-100): 1.
the invention further provides application of the O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative in the field of pesticides or medical materials.
The reaction equation involved in the method of the invention:
compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the synthesis method of the invention does not use catalyst and ligand, and the used raw materials are nontoxic, cheap and easy to obtain; the reaction has good adaptability to functional groups, wide adaptability to substrates and high product yield;
(2) the synthesis method can be used for scale-up to gram-scale production, is simple and safe to operate, has mild reaction conditions, and has good industrial application prospect;
(3) the product obtained by the invention has wide application in the fields of pesticide, medicine and material.
Drawings
FIG. 1 is a hydrogen spectrum of the product obtained in examples 1 to 5;
FIG. 2 is a carbon spectrum of the product obtained in examples 1 to 5;
FIG. 3 shows fluorine spectra of the products obtained in examples 1 to 5.
Detailed description of the invention
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under the air atmosphere, adding 0.4 mmol of acetophenone oxime, 0.6 mmol of potassium carbonate, 0.6 mmol of alpha-trifluoromethylstyrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), and 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping heating and stirring, cooling to room temperature, adding water, extracting the reaction solution with ethyl acetate, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing the solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 35%.
Example 2
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under nitrogen atmosphere, adding 0.4 mmol of acetophenone oxime, 0.6 mmol of potassium tert-butoxide, 0.6 mmol of alpha-trifluoromethylstyrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP) and 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping heating and stirring, cooling to room temperature, adding water and ethyl acetate to extract a reaction solution, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing a solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 88%.
Example 3
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under the nitrogen atmosphere, adding 0.4 mmol of acetophenone oxime, 0.6 mmol of lithium tert-butoxide, 0.6 mmol of alpha-trifluoromethylstyrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP) and 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping heating and stirring, cooling to room temperature, adding water and ethyl acetate to extract the reaction solution, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing the solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 100: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 82%.
Example 4
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under the nitrogen atmosphere, adding 0.4 mmol of acetophenone oxime, 0.6 mmol of sodium tert-butoxide, 0.6 mmol of alpha-trifluoromethylstyrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP) and 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping heating and stirring, cooling to room temperature, adding water, extracting the reaction solution with ethyl acetate, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing the solvent, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of the used column chromatography eluent is 5: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 86%.
Example 5
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under nitrogen atmosphere, adding 0.4 mmol of acetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethylstyrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping heating and stirring, cooling to room temperature, adding water and ethyl acetate to extract a reaction solution, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing a solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 90%.
The structural characterization data of the product obtained in examples 1-5 are as follows:
1H NMR(400MHz,CDCl3)δ7.65(d,J＝7.4Hz,2H),7.57(d,J＝6.8Hz,2H),7.33–7.42(m,6H),5.30(brs,1H),4.79(d,J＝13.0Hz,1H),4.50(d,J＝13.0Hz,1H),2.19(s,3H)；
13C NMR(100MHz,CDCl3)δ157.9,135.4,135.2,129.9,128.6,128.6,128.3,126.3,126.1,124.9(q,1JF-C＝284.7Hz),78.2(q,2JF-C＝27.7Hz),75.0,12.9；
19F NMR(376MHz,CDCl3)δ-76.2(s,3F)；
IR(KBr):3370,3061,2935,1452,1174,1063cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C17H16F3NO2+H,324.1206；found,324.1210.
the structure of the product obtained is shown in the following formula:
example 6
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under nitrogen atmosphere, adding 0.4 mmol of p-methyl acetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethyl styrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP) and 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring the reaction system at room temperature for 12 hours, stopping stirring, adding water, extracting the reaction solution with ethyl acetate, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing the solvent, and separating and purifying by column chromatography to obtain the target product, wherein the volume ratio of the column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 77%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.64(d,J＝7.2Hz,2H),7.47(d,J＝7.6Hz,2H),7.38(m,3H),7.17(d,J＝7.6Hz,2H),5.39(brs,1H),4.77(d,J＝13.0Hz,1H),4.49(d,J＝13.0Hz,1H),2.35(s,3H),2.17(s,3H)；
13C NMR(101MHz,CDCl3)δ157.8,140.1,135.5,132.4,129.28,128.60,128.3,126.4,126.0,124.9(q,1JF-C＝284.4Hz),78.2(q,2JF-C＝27.7Hz),74.8,21.2,12.8；
19F NMR(376MHz,CDCl3)δ-76.2(s,3F)；
IR(KBr):3361,3051,2934,1441,1171,1062cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C18H18F3NO2+H,338.1362；found,338.1361.
the structure of the product obtained in this example is shown below:
example 7
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under the nitrogen atmosphere, adding 0.4 mmol of p-chlorophenyl glyoxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethylstyrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), and 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping stirring, cooling to room temperature, adding water and ethyl acetate to extract the reaction solution, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing the solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 85%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.64(d,J＝7.2Hz,2H),7.51(d,J＝8.0Hz,2H),7.327.42(m,5H),5.00(brs,1H),4.79(d,J＝12.8Hz,1H),4.50(d,J＝12.8Hz,1H),2.17(s,3H)；
13C NMR(101MHz,CDCl3)δ156.8,136.0,135.3,133.7,128.8,128.7,128.3,127.4,126.3,124.9(q,1JF-C＝284.7Hz),77.9(q,2JF-C＝27.8Hz),75.1,12.7；
19F NMR(376MHz,CDCl3)δ-76.2(s)；
IR(KBr):3397,3063,2936,1488,1171,1070cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C17H15ClF3NO2+H,358.0816；found,358.0819.
the structure of the product obtained in this example is shown below:
example 8
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under the nitrogen atmosphere, adding 0.4 mmol of p-bromoacetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethylstyrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping stirring, cooling to room temperature, adding water and ethyl acetate to extract a reaction solution, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing a solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 83%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.64(d,J＝7.6Hz,2H),7.50(d,J＝8.0Hz,2H),7.36–7.46(m,5H),5.00(brs,1H),4.79(d,J＝12.8Hz,1H),4.50(d,J＝12.8Hz,1H),2.17(s,3H)；
13C NMR(101MHz,CDCl3)δ156.9,135.3,134.1,131.8,128.7,128.3,127.6,126.3,124.3,124.9(q,1JF-C＝284.3Hz),78.0(q,2JF-C＝27.8Hz),75.2,12.7；
19F NMR(376MHz,CDCl3)δ-76.2(s)；
IR(KBr):3453,2930,1640,1382,1189,1069cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C17H15BrF3NO2+H,402.0311；found,402.0312.
the structure of the product obtained in this example is shown below:
example 9
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under the nitrogen atmosphere, adding 0.4 mmol of p-trifluoromethyl acetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethyl styrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), and 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping stirring, cooling to room temperature, adding water, extracting the reaction solution with ethyl acetate, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing the solvent, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of the used column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 89%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.62–7.70(m,6H),7.35–7.43(m,3H),4.83(brs,1H),4.83(d,J＝12.8Hz,1H),4.54(d,J＝12.8Hz,1H),2.22(s,3H)；
13C NMR(101MHz,CDCl3)δ156.7,138.7,135.2,131.7(q,2JF-C＝32.5Hz),128.8,128.4,126.5,126.3,125.5(q,3JF-C＝3.7Hz),124.9(q,1JF-C＝285.0Hz),123.9(q,1JF-C＝270.5Hz),77.9(q,2JF-C＝27.8Hz),75.4,12.8；
19F NMR(376MHz,CDCl3)δ-62.9(s),-76.3(s)；
IR(KBr):3416,3066,2939,1324,1158cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C18H15F6NO2+H,392.1080；found,392.1078.
the structure of the product obtained in this example is shown below:
example 10
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under the nitrogen atmosphere, adding 0.4 mmol of p-methylsulfonyl acetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethyl styrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), and 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping stirring, cooling to room temperature, adding water, extracting the reaction solution with ethyl acetate, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing the solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 95%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.94(d,J＝8.4Hz,2H),7.76(d,J＝8.4Hz,2H),7.64(d,J＝7.6Hz,2H),7.36–7.43(m,3H),4.85(d,J＝12.8Hz,1H),4.68(brs,1H),4.57(d,J＝12.8Hz,1H),3.05(s,3H),2.23(s,3H)；
13C NMR(101MHz,CDCl3)δ156.1,141.3,140.5,135.0,128.7,128.3,127.6,127.0,126.1,124.8(q,1JF-C＝284.4Hz),77.6(q,2JF-C＝27.8Hz),75.6,44.3,12.8；
19F NMR(376MHz,CDCl3)δ-76.2(s)；
IR(KBr):3457,3051,2935,1301,1161,1074cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C18H18F3NO4S+H,402.0981；found,402.0988.
the structure of the product obtained in this example is shown below:
example 11
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under nitrogen atmosphere, adding 0.4 mmol of p-iodoacetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethylstyrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), and 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping stirring, cooling to room temperature, adding water and ethyl acetate to extract a reaction solution, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing a solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 81%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.70(d,J＝7.6Hz,2H),7.63(d,J＝7.2Hz,2H),7.35–7.42(m,3H),7.30(d,J＝7.6Hz,2H),4.99(brs,1H),4.79(d,J＝12.8Hz,1H),4.50(d,J＝12.8Hz,1H),2.16(s,3H)；
13C NMR(101MHz,CDCl3)δ157.0,137.7,135.3,134.7,128.7,128.3,127.7,126.3,124.9(q,1JF-C＝284.3Hz),96.2,78.0(q,2JF-C＝27.7Hz),75.2,12.6；
19F NMR(376MHz,CDCl3)δ-76.2(s)；
IR(KBr):3391,3062,2933,1472,1171,1062cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C17H15F3INO2+H,450.0172；found,450.0173.
the structure of the product obtained in this example is shown below:
example 12
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under the nitrogen atmosphere, adding 0.4 mmol of p-methoxy acetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethyl styrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping stirring, cooling to room temperature, adding water and ethyl acetate to extract a reaction solution, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing a solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 40: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 78%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.65(d,J＝7.2Hz,2H),7.53(d,J＝8.4Hz,2H),7.347.42(m,3H),6.89(d,J＝8.4Hz,2H),5.40(brs,1H),4.76(d,J＝12.8Hz,1H),4.48(d,J＝12.8Hz,1H),3.81(s,3H),2.17(s,3H)；
13C NMR(101MHz,CDCl3)δ161.1,157.5,135.6,128.7,128.3,127.7,127.6,126.4,125.0(q,1JF-C＝284.4Hz),114.0,78.2(q,2JF-C＝27.7Hz),74.9,55.4,12.8；
19F NMR(376MHz,CDCl3)δ-76.2(s)；
IR(KBr):3370,3062,2939,1471,1171,1054cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C18H18F3NO2+H,354.1312；found,354.1321.
the structure of the product obtained in this example is shown below:
example 13
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under the nitrogen atmosphere, adding 0.4 mmol of 3, 4-dimethyl acetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethyl styrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), and 2 ml of N, N-dimethyl formamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping heating and stirring, cooling to room temperature, adding water, extracting the reaction solution with ethyl acetate, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing the solvent, and carrying out column chromatography separation and purification to obtain the target product, wherein the volume ratio of column chromatography eluent is 40: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 77%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.65(d,J＝7.6Hz,2H),7.357.41(m,4H),7.30(d,J＝8.0Hz,1H),7.12(d,J＝8.0Hz,1H),5.35(brs,1H),4.77(d,J＝13.2Hz,1H),4.49(d,J＝13.2Hz,1H),2.27(s,3H),2.26(s,3H),2.16(s,3H)；
13C NMR(101MHz,CDCl3)δ158.0,138.8,136.9,135.5,132.8,129.8,128.6,128.3,127.2,126.4,125.0(q,1JF-C＝284.7Hz),123.7,78.2(q,2JF-C＝27.8Hz),74.8,19.8,19.6,12.8；
19F NMR(376MHz,CDCl3)δ-76.2(s)；
IR(KBr):3372,3059,2935,1450,1171,1059cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C19H20F3NO2+H,352.1519；found,352.1517.
the structure of the product obtained in this example is shown below:
example 14
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under nitrogen atmosphere, adding 0.4 mmol of benzophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethylstyrene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping heating and stirring, cooling to room temperature, adding water and ethyl acetate to extract a reaction solution, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing a solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 89%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.62(d,J＝6.8Hz,2H),7.32–7.42(m,11H),7.10(d,J＝6.8Hz,2H),5.11(brs,1H),4.75(d,J＝13.2Hz,1H),4.51(d,J＝13.2Hz,1H)；
13C NMR(101MHz,CDCl3)δ159.4,135.5,135.2,132.0,130.1,129.3,129.0,128.6,128.4,128.3,128.1,128.1,124.8(q,1JF-C＝284.5Hz),78.1(q,2JF-C＝27.8Hz),75.1；19F NMR(376MHz,CDCl3)δ-76.5(s)；
IR(KBr):3392,3058,2930,1449,1168,1064cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C22H18F3NO2+H,386.1362；found,386.1364.
the structure of the product obtained in this example is shown below:
example 15
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under nitrogen atmosphere, adding 0.4 mmol of acetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethyl p-methyl phenyl ethylene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), 2 ml of N, N-dimethyl formamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping heating and stirring, cooling to room temperature, adding water, extracting the reaction solution with ethyl acetate, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing a solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 81%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.58(d,J＝6.8Hz,2H),7.53(d,J＝8.0Hz,2H),7.32–7.41(m,3H),7.21(d,J＝7.6Hz,2H),5.15(brs,1H),4.77(d,J＝12.8Hz,1H),4.489(d,J＝12.8Hz,1H),2.35(s,3H),2.21(s,3H)；
13C NMR(101MHz,CDCl3)δ157.8,138.5,135.3,132.5,129.9,129.0,128.6,126.2,126.1,125.0(q,1JF-C＝284.7Hz),78.0(q,2JF-C＝27.7Hz),75.0,21.0,12.9；
19F NMR(376MHz,CDCl3)δ-76.3(s)；
IR(KBr):3354,3070,2932,1440,1170,1063cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C18H18F3NO2+H,338.1362；found,338.1366.
the structure of the product obtained in this example is shown below:
example 16
This example provides an O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative and a method for synthesizing the same, including the following steps:
under nitrogen atmosphere, adding 0.4 mmol of acetophenone oxime, 0.6 mmol of cesium carbonate, 0.6 mmol of alpha-trifluoromethyl p-methoxyphenyl ethylene, 0.6 mmol of tert-butyl hydroperoxide (TBHP), 2 ml of N, N-dimethylformamide into a 25 ml reaction bottle provided with a reflux condenser, stirring and reacting the reaction system at room temperature for 12 hours, stopping stirring, cooling to room temperature, adding water and ethyl acetate to extract a reaction solution, carrying out reduced pressure rotary evaporation on an ethyl acetate layer, removing a solvent, and carrying out column chromatography separation and purification to obtain a target product, wherein the volume ratio of column chromatography eluent is 50: 1 petroleum ether: ethyl acetate mixed solvent; the yield of the product was 71%.
The structural characterization data for the product obtained in this example are as follows:
1H NMR(400MHz,CDCl3)δ7.55–7.59(m,4H),7.35–7.41(m,3H),6.93(d,J＝8.4Hz,2H),5.26(brs,1H),4.76(d,J＝13.2Hz,1H),4.48(d,J＝12.8Hz,1H),3.81(s,3H),2.21(s,3H)；
13C NMR(101MHz,CDCl3)δ159.8,157.8,135.3,129.9,128.6,127.7,127.4,126.1,125.0(q,1JF-C＝284.5Hz),113.7,77.9(q,2JF-C＝27.7Hz),74.9,55.2,12.9；
19F NMR(376MHz,CDCl3)δ-76.6(s)；
IR(KBr):3419,3072,2944,1510,1169,1056cm-1；
HRMS(ESI,m/z):[M+H]+Calcd.for C18H18F3NO3+H,354.1312；found,354.1320.
the structure of the product obtained in this example is shown below:
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative is characterized in that the structure is as follows:
wherein R is1Is phenyl, p-bromophenyl, p-chlorophenyl, m-chlorophenyl, o-chlorophenyl, p-fluorophenyl, m-fluorophenyl, o-fluorophenyl, p-iodophenyl, p-tolyl (p-methylphenyl), m-tolyl, p-methoxyphenyl, m-methoxyphenyl, p-methylthiophenyl, p-trifluoromethylphenyl, p-methylsulfonylphenyl, p-carbomethoxyphenyl, p-cyanophenyl, 3, 4-dimethylphenyl, 3, 4-methylenedioxyphenyl, styryl, 1-tetrahydronaphthyl, 2-naphthyl, 2-furyl, 2-thienyl or 2-pyridyl;
R2is phenyl, methyl, ethyl or tert-butyl;
R3is phenyl, p-bromophenyl, p-chlorophenyl, p-fluorophenyl, p-tolyl (p-methylphenyl), p-methoxyphenyl, p-trifluoromethylphenyl, p-tert-butylphenyl, p-morpholinophenyl, 3, 4-dimethylphenyl, 2-naphthyl, 3-benzothienyl or 3-pyridyl.
2. The O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative of claim 1 having any one of the following structural formulas:
3. the method for synthesizing O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives according to claim 1 or 2, which comprises the steps of: in alkali and organic solvent I, uniformly mixing ketoxime compound, alpha-trifluoromethyl styrene compound and tert-butyl hydroperoxide (TBHP) to obtain reactant, then reacting, and carrying out subsequent purification treatment after reaction to obtain the O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative.
4. The method for synthesizing O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives according to claim 3, wherein:
the ketoxime compound is
The alpha-trifluoromethyl styrene compound is
5. The method for synthesizing O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives according to claim 3, wherein:
the alkali is one or more than two of cesium carbonate, potassium tert-butoxide, lithium tert-butoxide and sodium tert-butoxide;
the organic solvent I is one or more than two of N, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, N-methylpyrrolidone and acetonitrile.
6. The method for synthesizing O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives according to claim 3, wherein:
in the reactants, the molar ratio of the ketoxime compound to the alpha-trifluoromethyl styrene compound is 1: 1-1: 3;
in the reactant, the molar ratio of the ketoxime compound to tert-butyl hydroperoxide (TBHP) is 1: 1-1: 3;
in the reactant, the molar ratio of the ketoxime compound to the alkali is 1: 1-1: 3.
7. The method for synthesizing O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives according to claim 6, wherein:
in the reactants, the molar ratio of the ketoxime compound to the alpha-trifluoromethyl styrene compound is 1: 1.5;
in the reactants, the molar ratio of the ketoxime compound to tert-butyl hydroperoxide (TBHP) is 1: 1.5;
in the reactants, the molar ratio of the ketoxime compound to the alkali is 1: 1.5.
8. The method for synthesizing O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives according to claim 3, wherein: the reaction temperature is room temperature, the reaction time is 12h, and the reaction is carried out in the atmosphere of air or nitrogen.
9. The method for synthesizing O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives according to claim 3, wherein: the subsequent purification treatment is that after the reaction is finished, water and an organic solvent II are added to extract a reaction solution, an organic layer is subjected to reduced pressure rotary evaporation to remove the solvent, a crude product is obtained, and the crude product is subjected to column chromatography purification to obtain the O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative;
the organic solvent II is ethyl acetate, dichloromethane or diethyl ether;
the column chromatography purification refers to the purification by using petroleum ether: and (3) performing column chromatography purification by using a mixed solvent of ethyl acetate as an eluent, wherein the weight ratio of petroleum ether: the volume ratio of the ethyl acetate is (5-100): 1.
10. use of O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivatives according to claim 1 or 2, characterized in that: the O- (2-trifluoromethyl-2-hydroxyethyl) oxime ether derivative is used for pesticides or medical materials.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812035A (en) * | 2021-02-01 | 2021-05-18 | 闽江学院 | Fluoroacetaldehyde-oxygen-aryl oxime compound and synthesis method thereof |
| CN114014779A (en) * | 2021-12-14 | 2022-02-08 | 安徽师范大学 | Bisaryl oxime ether compound and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5434306A (en) * | 1993-11-25 | 1995-07-18 | Ciba-Geigy Corporation | Process for the preparation of O-substituted oximes |
| CN1114645A (en) * | 1994-05-05 | 1996-01-10 | 巴斯福股份公司 | O-(oximino) ethylcyclohexenone oxime ethers and their use as herbicides |
| CN1134420A (en) * | 1995-02-24 | 1996-10-30 | 巴斯福股份公司 | 5-tetrahydropyranone cyclohexenone oxime ethers and their use as herbicides |
| WO2015199065A1 (en) * | 2014-06-24 | 2015-12-30 | 日本曹達株式会社 | Pyridine compound and use of same |
| CN108976170A (en) * | 2018-08-14 | 2018-12-11 | 华南理工大学 | A kind of 5- trifluoromethyl -4H- imidazoline -4- ketone derivatives and synthetic method |
| CN109232310A (en) * | 2018-09-25 | 2019-01-18 | 华南理工大学 | A kind of trifluoroacetyl group replaces hydazone derivative and its synthetic method |
| CN109280025A (en) * | 2018-09-30 | 2019-01-29 | 上海大学 | O-(N- ethyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives and preparation method thereof |
| CN109651191A (en) * | 2019-01-07 | 2019-04-19 | 华南理工大学 | A kind of difluoromethyl oxime ether derivatives and its synthetic method |
-
2019
- 2019-09-20 CN CN201910891936.0A patent/CN110642748B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5434306A (en) * | 1993-11-25 | 1995-07-18 | Ciba-Geigy Corporation | Process for the preparation of O-substituted oximes |
| CN1114645A (en) * | 1994-05-05 | 1996-01-10 | 巴斯福股份公司 | O-(oximino) ethylcyclohexenone oxime ethers and their use as herbicides |
| CN1134420A (en) * | 1995-02-24 | 1996-10-30 | 巴斯福股份公司 | 5-tetrahydropyranone cyclohexenone oxime ethers and their use as herbicides |
| WO2015199065A1 (en) * | 2014-06-24 | 2015-12-30 | 日本曹達株式会社 | Pyridine compound and use of same |
| CN108976170A (en) * | 2018-08-14 | 2018-12-11 | 华南理工大学 | A kind of 5- trifluoromethyl -4H- imidazoline -4- ketone derivatives and synthetic method |
| CN109232310A (en) * | 2018-09-25 | 2019-01-18 | 华南理工大学 | A kind of trifluoroacetyl group replaces hydazone derivative and its synthetic method |
| CN109280025A (en) * | 2018-09-30 | 2019-01-29 | 上海大学 | O-(N- ethyl -2,5- dicarbapentaborane pyrrolidinyl) -one oxime ether derivatives and preparation method thereof |
| CN109651191A (en) * | 2019-01-07 | 2019-04-19 | 华南理工大学 | A kind of difluoromethyl oxime ether derivatives and its synthetic method |
Non-Patent Citations (1)
| Title |
|---|
| HAO ZENG等: "Three component hydroxyletherification and hydroxylazidation of (trifluoromethyl)alkenes: access to a-trifluoromethyl b-heteroatom substituted tertiary alcohols", 《CHEMICAL COMMUNICATIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812035A (en) * | 2021-02-01 | 2021-05-18 | 闽江学院 | Fluoroacetaldehyde-oxygen-aryl oxime compound and synthesis method thereof |
| CN114014779A (en) * | 2021-12-14 | 2022-02-08 | 安徽师范大学 | Bisaryl oxime ether compound and preparation method thereof |
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